Exquisite chemistries of meso-pentafluorophenyl and meso-(2,6-dichlorophenyl) dipyrromethanes

Abstract

meso-Aryl dipyrromethanes are important building blocks to create various practical molecules, and the electron-withdrawing effect of the meso-aryls can play an important role in improving/controlling their reactivities in further reactions: meso-Pentafluorophenyl and meso-(2,6-dichlorophenyl) substituted dipyrromethanes towards the associating dipyrrins and other derivatives have been investigated, in which coordination with different transition metals followed by the dissociation of the metal coordination by interruption of proton and halide ions have been verified. Furthermore, simple DDQ-oxidations of the dipyrromethanes have afforded DDQ-dipyrrin adducts which were delivered to distinctly advanced molecular rearrangements in the presence of acid and base. Vinylene bisdipyrrin compounds, obtained in the reactions of DDQ-dipyrrin adducts with a Lewis base triethylamine, have produced expanded porphyrinoid bis-nickel complexes during the metalation procedure with nickel acetate, while a cobalt metalation of the vinylene bisdipyrrin compounds resulted in an isolation of diamagnetic octahedral cobalt(III) complex. Moreover, meso-pentafluorophenyl and meso-(2,6-dichlorophenyl) dipyrromethanes have been useful platforms to accomplish size-controlled series of meso-aryl-substituted expanded porphyrins and easy separation/purification of selective meso-aryl expanded porphyrins, in which advanced metal complexes and various fascinating properties and reactivities admitting moderate functional molecules have arisen.